Epoxy fatty hydrazides and process of preparing the same



United States Patent EPOXY FATTY HY DRAZIDES AND PROCESS OF PREPARING THE SAME Thomas Wagner Findley, La Grange, 111., assignor to Swgift 8: Company, Chicago, Ill., a corporation of Illino s No Drawing. Application October 7, 1955 Serial No. 539,274

9 Claims. (Cl. 260-348) This invention in general relates to new compositions of matter and methods for preparation thereof. More specifically, the invention relates to epoxy fatty hydrazides and to a method for their preparation.

Prior attempts to react hydrazine and epoxy fatty acids have been reported as yielding a cyclic hydrazino fatty acid having the configuration NH-NH in the fatty chain. Bauer and B'zihr, J. Prakt Chem., volume 122, pp. 201213 (1929). The reaction of this invention difiers in that the end product is an epoxy fatty hydrazide of the formula wherein R is hydrogen or an aliphatic radical, R is an aliphatic radical, and the sum of the carbons R and R is at least 7.

Therefore, it is an object of this invention to provide a new composition of matter.

Another object of this invention is to provide epoxy fatty hydrazides.

A further object of this invention is to provide a method for producing epoxy fatty hydrazides.

Other objects will be apparent to one skilled in the art from the following detailed description.

In general, the present invention comprises a low temperature reaction of excess hydrazine with epoxy fatty acid esters. The epoxy fatty acid esters may be esters of monohydric or polyhydric alcohols. Epoxidized glyceride oils such as epoxidized soybean oil are practical raw materials for preparation of the hydrazides of this invention. If a more pure epoxy fatty hydrazide is desired, hydrazine may be reacted with an ester of a specific epoxy fatty acid such as methyl epoxy stearate, methyl epoxy palmitate, methyl di-epoxy stearate, etc.

Included Within the scope of this invention are epoxy fatty hydrazides having a carbon chain length of 10-22. The fatty acid portion of the epoxy hydrazides of the present invention is derived from naturally occurring fats having a substantial portion of unsaturated acids, i.e., monoethenoid, diethenoid, and triethenoid acids which may be epoxidized by an oxidizing agent. The unsaturated acids of most common occurrence in fatty glycerides are oleic (cis-A9,10-octadecenoic), palmitoleic (A9,10- hexadecenoic), linoleic (cis-A9,10-cisAl2,l3 octadecadienoic), linolenic (A9,10,12,13,15,16- octadecatrienoic), and ricinoleic (12-hydroxy-A9,l0-octadecenoic) acids. Other fatty acids of less common occurrence include A9,10- and A4,5-decenoic acid; A3,4-, A4,5-, and A9,10-dodecenoic acid; A9,10-tetradecenoic acid (myristoleic acid), and A4,5- and A5,6-tetradecenoic acid; cis- A6,7-octadecenoic acid (petroselenic acid) and A11,12- octadecenoic acid (vaccenic acid); A9,10-eicosenoic acid 2,892,848 Patented June 30, 1959 (gadoleic acid) and A11,12-eicosenoic acid; A6,7,10,11, 14,15-hexadecatrienoic acid; and cis-Al3,14-docosenoic acid (erucic acid). p

The esters are first epoxidized with an oxidizing agent such as peracetic acid or hydrogen peroxide in the presence of a catalyst such as formic acid at temperatures of '40-100 C. by procedures well known in the art. The epoxidized esters are then reacted with hydrazine hydrate in the manner previously described.

The more important hydrazides, from a commercial viewpoint, due to the common occurrence of the fatty radicals in natural glycerides, include 9,10-epoxy stearic hydrazide, 9,10-epoxy palmitic hydrazide, monoepoxy oleic hydrazide or epoxy octadecenoic hydrazide, 9,10, 12,13-di-epoxy stearic hydrazide, monoepoxy linoleic hydrazide or monoepoxy octadecadienoic hydrazide, diepoxy oleic hydrazide, 9,10,12,13,15,16-triepoxy stearic hydrazide, and IZ-hydroxy, 9,10-epoxy stearic hydrazide. The extent of epoxidation and the position of the epoxy groups in the diand tri-ethenoid acid esters cannot be definitely ascertained. For example, it appears that epoxidation of a di-ethenoid acid ester, such as linoleic ester, gives a mixture of monoepoxy oleic esters with some epoxy in the 9,10 position and some in the 12,13 position, as well as di-epoxy stearic esters. A preponderance of the mono-epoxy or di-epoxy acid esters is obtained largely by the control of the molar concentration of the oxidizing agent.

Example I Ten grams of epoxidized soybean oil (5.21% epoxy oxygen) and 2 ml. of hydrazine hydrate are mixed and heated at C. for sixteen hours. The mixture becomes homogeneous and solidifies on cooling at room temperature. The hydrazide mixture is insoluble in ether. The hydrazide of mixed epoxy fatty acids of soybean oil is purified by water washing to remove glycerine and excess hydrazine. The epoxy fatty hydrazides formed by the above reaction using soybean oil are primarily hydrazides of epoxidized oleic, linoleic, and linolenic acids.

Example II One-tenth mol of methyl epoxy stearate and 0.11 mol of hydrazine hydrate are mixed and held on a water bath at 90 C. As the reaction proceeds, the methanol formed boils off. The reaction is complete in about eight hours. The product solidifies as a light colored solid at room temperature. It is purified by water washing. Upon recrystallization in ethanol, substantially pure epoxy stearic hydrazide is recovered as colorless crystals.

The epoxy fatty hydrazides of this invention may be applied to quack grass for growth control. Application of 30 to gallons of an oil and water emulsion containing about 30 lbs. of the epoxy fatty hydrazides to one acre of quack grass in early spring after the grass has obtained a height of about 4 or more inches will check the growth and spreading of quack grass.

Obviously, many modifications and variations of the invention as hereinbefore set forth may be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.

I claim:

1. As a new composition of matter, 9,10-epoxy stearic hydrazide.

2. As a new composition of matter, 9,10-epoxy palmitic hydrazide.

3. As a new composition of matter, epoxy octadecenoic hydrazide.

4. As a new composition of matter, 9,10,12,13-diepoxy stearic hydrazide.

5. As a new composition of matter, monoepoxy octadecadienoic hydrazide.

6. The hydrazides of epogridized ethenoid fatty acids, said, ethenoid fatty acids ,haying a carbonv chain; length fi qlellx nd t in HQXi1'al1 gr ups-i 7. "The hydrazides of "soybean fatty acids containing, ,Q iranergroup 8: A methodforproducingan oxiranercontaining fatty hydrazidehfrom esters.- QL'OXiranecQntaining fatty acids;

thesteps whichcornpriseg heating at a low reaction tern 10 eratureepoxidizedj ethenoid fatty acid esters, theacid part of said 'esters containing 1-3 oxiranegroups and havi x r acarbpn chainl length of. 10-22, with an,excess; of hydrazine, and removing the excess hydrazine from the ma net pr'os nca assasee 9. In a method for producing an oxirane-containing fatty hydrazide, the step which comprises: heating hydrazine with esters of ethenoid fatty acids, said acids containing 1-3 oxirane groups and having a carbon chain length of 10-22, at atlow reaction temperature to form oXirane-containing fatty hydrazides.

OTHER REFERENCES Wagner" and* Zookz; Synthetic Org.- Chem., p. 569 

6. THE HYDRAZIDES OF EPOXIDIZED ETHENOID FATTY ACIDS, SAID ETHENOID FATTY ACIDS HAVING A CARBON CHAIN LENGTH OF 10-22 AND CONTAINING 1-3 OXIRANE GROUPS.
 8. A METHOD FOR PRODUCING AN OIXRANE-CONTAINING FATTY HYDRAZIDE FROM ESTERS OF OXIRANE-CONTAINING FATTY ACIDS, THE STEPS WHICH COMPRISE: HEATING AT A LOW REACTION TEMPERATURE EPOXIDIZED ETHENOID FATTY ACID ESTERS, THE ACID PART OF SAID ESTERS CONTAINING 1-3 OXIRANE GROUPS AND HAVING A CARBON CHAIN LENGTH OF 10-22, WITH AN EXCESS OF HYDRAZINE, AND REMOVING THE EXCESS HYDRAZINE FROM THE REACTION PRODUCT. 